The ESR spectra of three diphosphorylated pyrrolidinoxyl radicals have been studied over a large temperature range. While for the trans 2,5-disubstituted compound 1 no line width alternation was found ... [more ▼]

The ESR spectra of three diphosphorylated pyrrolidinoxyl radicals have been studied over a large temperature range. While for the trans 2,5-disubstituted compound 1 no line width alternation was found, for the 2,2-disubstituted compounds 2 and 3, dramatic changes in the spectra were observed as a function of the temperature. These changes were explained by a four-site chemical exchange model including both ring inversion and hindered rotation around the carbon-phosphorus bonds. For radical 3, the presence of additional 5,5-dimethyl substitution can completely block rotations around carbon-phosphorus bonds for certain ring geometries, while for other ring conformations chemical exchange still occurs through combined inversionrotation processes. An effective two-site model composed of nonequivalent sites and a superposition model composed of a pair of exchanging conformers and a pair of nonexchanging conformers were used to simulate spectrum variations. A satisfactory fit was obtained over the entire temperature range investigated. From the temperature dependence of the exchange frequencies the potential barriers for ring inversion (27 kJ/mol), for combined inversion-rotation (11 kJ/mol), and for rotation around the carbon-phosphorus bonds (14 kJ/mol) were estimated. [less ▲]

There is a characteristic decrease in glucose metabolism in associative frontal and temporo-parietal cortices of patients suffering from Alzheimer's disease (AD). The decrease in metabolism might result ... [more ▼]

There is a characteristic decrease in glucose metabolism in associative frontal and temporo-parietal cortices of patients suffering from Alzheimer's disease (AD). The decrease in metabolism might result from local neuronal loss or from a decrease of synaptic activity. We measured in vivo [11C]methionine accumulation into proteins with positron emission tomography (PET) to assess cortical tissue loss in AD. Both global regional activity and compartmental analysis were used to express [11C]methionine accumulation into brain tissue. Glucose metabolism was measures with [18F]fluorodeoxyglucose and autoradiographic method. Combined studies were performed in 10 patients with probable AD, compared to age-matched healthy volunteers. There was a significant 45% decrease of temporo-parietal glucose metabolism in patients with AD, and frontal metabolism was lowered in most patients. Temporo-parietal metabolism correlated to dementia severity. [11C]methionine incorporation into temporo-parietal and frontal cortices was not significantly decreased in AD. There was no correlation with clinical symptoms. Data suggest that regional tissue loss, assessed by the decrease of [11C]methionine accumulation, is not sufficient to explain cortical glucose hypometabolism, which reflects, rather, reduced synaptic connectivity. [less ▲]

BACKGROUND: Gene therapy is a novel approach for the treatment of cancers, and tumours disseminated in the peritoneal cavity are suitable for in situ delivery of a therapeutic gene. AIMS: The efficacy of ... [more ▼]

BACKGROUND: Gene therapy is a novel approach for the treatment of cancers, and tumours disseminated in the peritoneal cavity are suitable for in situ delivery of a therapeutic gene. AIMS: The efficacy of a therapy combining a suicide gene (herpes simplex virus type I thymidine kinase (HSV-TK)) and cytokine genes was investigated in a model of peritoneal carcinomatosis induced by colon carcinoma cells in syngeneic rats. MATERIAL AND METHODS: Pre-established macroscopic tumours in BDIX rats were treated by intraperitoneal injections of retrovirus producing cells (FLYA13 TK, FLYA13 granulocyte macrophage-colony stimulating factor (GM-CSF), FLYA13 interleukin 12 (IL-12)) and ganciclovir (GCV). RESULTS: TK/GCV treated animals showed a slight increase in survival time (72 days) compared with the control group (63 days) while the association of cytokine and TK/GCV gene therapy resulted in significantly improved survival, with a large proportion of animals remaining tumour free on day 480 (60% and 40% for TK/GCV/GM-CSF and TK/GCV/IL-12 treated animals, respectively). Histological analysis of treated animals showed that the remaining tumour nodes were infiltrated by mononuclear cells but no major differences were observed between the various treatments. Immunohistochemical analysis revealed that lymphoid CD4(+) and CD8(+) T cells as well as macrophages accumulated outside untreated tumour nodes while CD8(+) and CD25(+) activated T cells and macrophages heavily infiltrated the tumours after the different treatments. CONCLUSIONS: Our data indicate that combined suicide and cytokine gene therapy is a powerful approach for the treatment of macroscopic peritoneal carcinomatosis. [less ▲]

We report a combined theoretical and experimental study of the interaction between a series of transition metals (Ni, Cu, Zn) and acrylonitrile. We demonstrate experimentally that the transition metal has ... [more ▼]

We report a combined theoretical and experimental study of the interaction between a series of transition metals (Ni, Cu, Zn) and acrylonitrile. We demonstrate experimentally that the transition metal has a selective role in the grafting of electropolymerized acrylonitrile. Nickel and copper substrates support the formation of a polyacrylonitrile film, while zinc does not. Quantum chemical calculations indicate that acrylonitrile molecules form π-d bonds with Ni and Cu atoms, but do not react chemically with a Zn atom, in qualitative agreement with the experiment. Computational results also show that the electron affinity is significantly increased upon chemisorption, promoting radical anion species at the metal surface as initiators for polymerization. [less ▲]

Hepatorenal syndrome (HRS) is a severe complication of liver failure with high mortality. The pathogenesis of this reversible functional renal failure is not yet clearly understood. Diagnosis is based ... [more ▼]

Hepatorenal syndrome (HRS) is a severe complication of liver failure with high mortality. The pathogenesis of this reversible functional renal failure is not yet clearly understood. Diagnosis is based upon the association of clinical and biological criteria. A patient was admitted to our institution for severe liver failure secondary to an exacerbation of cirrhosis, where he developed a fulminant hepatorenal syndrome. Both, the renal and hepatic failure were successfully treated by orthotopic liver transplantation. Special attention was paid to the immunosuppressive treatment with Cyclosporine whose use, we believe, should be delayed until function has partially recovered. [less ▲]

BACKGROUND: This study evaluated the A-Line Autoregressive Index (AAI) response to surgical stimulation during lumbar arthrodesis, as an estimate of the anti-nociceptive component of a Bispectral Index ... [more ▼]

BACKGROUND: This study evaluated the A-Line Autoregressive Index (AAI) response to surgical stimulation during lumbar arthrodesis, as an estimate of the anti-nociceptive component of a Bispectral Index (BIS) guided anaesthesia combined with epidural analgesia. METHODS: An epidural catheter was inserted in 23 patients allocated randomly to receive ropivacaine plus clonidine (Group R) or normal saline (Group S) epidurally. General anaesthesia was induced with propofol, cis-atracurium and a remifentanil infusion that was stopped 3 min after tracheal intubation, and maintained using sevoflurane to keep BIS at 50 (range 40-60). Mean arterial pressure, heart rate, end-tidal sevoflurane, BIS and AAI were analysed from 2 min before to 17 min after surgical incision. RESULTS: While BIS was maintained at 50, AAI significantly increased from a 2 min averaged value of 12 (4) to 21 (7) in Group S within the first 5 min after surgical incision, but did not change in Group R. Maximum AAI values reached during the study period were significantly higher in Group S than in Group R [38 (12) and 27 (10), respectively]. Binary logistic regression analysis allowed the calculation of AAI threshold values above which the probability of predominant nociception over anti-nociception was higher than 95%. At 1 MAC sevoflurane concentration, a 2 min averaged AAI of 35 or an AAI peak value of 62 were associated with such a probability. CONCLUSIONS: During a BIS-guided constant level of hypnosis, AAI response to the onset of surgical stimulation significantly differs according to the analgesic regimen. Further studies are needed to refine the estimation of sensitivity and specificity of this variable in assessing the balance between nociception and anti-nociception during general anaesthesia. [less ▲]

Disulfide bonds are post-translational modifications (PTMs) often found in peptides and proteins. They increase their stability towards enzymatic degradations, and provide the structure and (consequently ... [more ▼]

Disulfide bonds are post-translational modifications (PTMs) often found in peptides and proteins. They increase their stability towards enzymatic degradations, and provide the structure and (consequently) the activity of such folded proteins. The characterization of disulfide patterns, i.e the cysteine connectivity, is crucial to achieve a global picture of the active conformation of the protein of interest. Electron Transfer Dissociation (ETD) constitutes a valuable tool to cleave the disulfide bonds in the gas phase, avoiding chemical reduction/alkylation in solution. To characterize the cysteine pairing, the present work proposes (i) to reduce by ETD one of the two disulfide bridges of model peptides , resulting in the opening of the cyclic structures, (ii) to separate the generated species by ion-mobility and, (iii) to characterize the species using CID. Results of this strategy applied to several peptides show different behaviors depending on the connectivity. The loss of SH• radical species, observed for all the peptides, confirms the cleavage of the disulfides during the ETD process. [less ▲]

in Diop, Salif; Barusseau, Jean-Paul; Descamp, Cyr (Eds.) The Land/Ocean Interactions in the Coastal Zone of West and Central Africa, Estuaries of the World (2014)

Saltwater contamination constitutes a serious problem in Saloumestuary, due to the intermittent and reverse tide flows of the Saloum River. This phenomenon is caused by the runoff deficit, which forces ... [more ▼]

Saltwater contamination constitutes a serious problem in Saloumestuary, due to the intermittent and reverse tide flows of the Saloum River. This phenomenon is caused by the runoff deficit, which forces the advance of saltwater 60 km upstream, contaminating surface water and thus causing the degradation of biodiversity and large areas of agricultural soils in this region. The present study aims to evaluate the consequences of saltwater contamination in the last three decades in this estuary by assessing the land-cover dynamics. Thus, latter consists of tracking the landscape-changing process over time to identify land-cover transitions. These transitions are closely related to the ecosystem-setting condition and can be used to assess the combined impacts of both natural and human-induced phenomena over a given period of time. In this study, special attention was given to mangrove degradation and to temporal progression of the salty barren soils locally called ‘‘tan’’. The loss of mangrove areas to tan and the general increase in salty barren soil areas can reflect the increase in the level of salinization in the study area over the time period under consideration. To fulfill this objective, four Landsat satellite images from the same season in the years 1984, 1992, 1999, and 2010 were used to infer time series land-use and land-cover maps of the Saloumestuary area. In addition to satellite imagery, rainfall records were used to evaluate climatic variation in terms of high-to-low precipitation during the time span considered. Spectral analysis indicated that from 1984 to 2010, mangroves and savanna/ rain-fed agriculture are converted to ‘‘tan’’ (denuded and salty soils). In addition, these results showed that significant changes in land use/land cover occur within the whole estuary system and reflecting therefore environmental degradation, such as land desertification and salinization, and vegetation degradation which reflect the advanced of salinity [less ▲]

Trace metal monitoring in marine organisms and their living habitats permit to trace chronic or acute contaminations of marine ecosystems due to human activities. While dissolved trace metal ... [more ▼]

Trace metal monitoring in marine organisms and their living habitats permit to trace chronic or acute contaminations of marine ecosystems due to human activities. While dissolved trace metal concentrations give us an overall and punctual view over biota contamination status, bioindicator species put their bioavailable and possible toxic fraction in an obvious. However, difficulties mainly inherent to metal measurements in seawater lead field ecotoxicologists to study marine pollution essentially through the use of bioindicators alone. The technique of diffusive gradients in thin films (DGT) for the measurement of trace metals in aqueous solutions was introduced in the mid-ninetieth by Davison and Zhang. This passive probe accumulates labile trace metal species in proportion to their bulk environmental concentrations by maintaining a negative gradient between the environment and an ion-exchange resin (Chelex). DGTs average natural water trace metal concentrations over the deployment period, concentrate them and avoid matrix interferences, notably due to dissolved salts in seawater. Their deployment in passive and experimental monitoring studies permits to reliably measure labile trace metal concentrations and, jointly analysed with bioindicators, to estimate their bioavailability to marine organisms. This combined approach DGT-bioindicator was investigated in Calvi Bay (Corsica) through three monitoring studies. (1) DGTs were deployed in Posidonia oceanica bed, a Mediterranean seagrass forming dense meadows from the surface down to 40 meters depth, to study seasonal, spatial and bathymetrical variations of labile trace metal concentrations within this meadow. These concentrations were analysed jointly with Posidonia trace metal contents in order to quantify their bioaccumulation towards this primary producer, taking into account the seagrass biological cycle. (2) Portions of Posidonia meadow were also in situ experimentally contaminated with a mix of dissolved metals to study seagrass kinetics of pollutant accumulation and decontamination. Thanks to DGTs deployed inside contaminated mesocosms throughout experiments, Posidonia responses to known metal concentrations could be precisely quantified. (3) The blue mussel Mytilus galloprovincialis is widely used in trace metal monitoring programs. Mussels, stored in conchylicultural pouches, were transplanted for 3 months in contrasted stations of Calvi Bay (e.g. aquaculture farm, sewer, etc.) in parallel with DGTs. Such as for Posidonia, the complementary utilization of DGTs and mussels permitted to describe water contamination levels at the scale of the Bay, and their bioaccumulation towards mussels. These 3 studies demonstrate the usefulness of DGTs to monitor labile trace metals in an ecological and ecosystemic approach, in parallel with marine organisms, both indicators furnishing different and complementary informations about ecosystem functioning. [less ▲]